WO2018024563A1 - Macromonomers containing polyisobutene groups, and homopolymers or copolymers thereof - Google Patents

Abstract

The invention relates to new macromonomers containing polyisobutene groups, and to the homopolymers or copolymers thereof.

Description

 Polyisobutene groups carrying macromonomers and their homopolymers or copolymers

Description The present invention describes novel polyisobutene-containing macromonomers and their homopolymers or copolymers.

Polyisobutene-bearing macromonomers based on e.g. Polyisobutenyl succinic anhydride (PIBSA) are already known, e.g. from WO 04/092227. In this case, however, structures with multiple functionalizations with succinic anhydride can be present in the preparation of the polyisobutenyl succinic anhydrides, which in a subsequent reaction with

(Meth) acrylic acid derivatives provide monomers having a (meth) acrylic acid functionality> 1 and thus lead to a proportion in the reaction mixture with crosslinking macromonomer structures. Furthermore, the reaction of PIBSA with alcohols produces a free acid group, which in addition reduces the hydrophobicity of the macromonomers and can lead to subsequent side reactions.

Polyisobutenes terminated with an OH function are valuable intermediates for the preparation of monofunctional macromers or macromonomers. It is the merit of Kennedy and Ivan to be the first to publish a synthetic route to such compounds via borane addition (Ivan, Kennedy Chang, J. Polym., Polym. Chem. Ed., 18: 3177 (1980)). The use of boranes for the production of technical polymers is too expensive, see also WO 14/090672. Also, the use of polyisobutenyl alcohols prepared via hydroformylation is not suitable for use in macromonomer manufacture due to the long reaction time at high temperatures in the presence of rhodium or cobalt catalysts and the comparatively low degree of functionalization with alcohol functionalities. See e.g. EP 277345.

Likewise obtained by reacting polyisobutene, for example, to polyisobuteneamines (commercially available as Kerocom® PIBA BASF) and then further to (meth) acrylamides macromonomers. However, these contain high-boiling solvents (up to 35%) and are therefore unusable for some solvent-free applications.

The use of the macromonomer structures based on the three precursors indicated here has already been described in EP 1899393 and once again illustrates the low degree of functionalization (<80%) of the macromonomers obtained therefrom. From K. Maenz, D. Stadermann, Angewandte Makromolekulare Chemie, 242 (1996) 183-197 it is known to esterify polyisobutene-carrying phenols with methacryloyl chloride From El Malins, C. Waterson, CR. Becer, J. Polym. Sc, Part A: Polymer Chemistry 2016, 54, 634-643, it is known to esterify polyisobutene-bearing phenols with acryloyl chloride and to homo- or copolymerize. It is known from WO 14/90672 to either ethoxylate polyols containing polyisobutene groups or to esterify them with (meth) acrylic acid. The products obtained can be used in the production of adhesives, adhesive raw materials, fuel and lubricant additives, as elastomers or as a basic component of sealing and sealing compounds. A disadvantage of the (meth) acrylates thus obtained is that their preparation requires the reaction of the free phenol with (meth) acryloyl chloride or anhydride. The reaction with acryloyl chloride is also disclosed explicitly in WO 14/90672 in one example. The esterification with (meth) acrylic acid or transesterification with (meth) acrylic esters, which is generally described in the description of WO 14/90672, gives the products in only poor yields. Furthermore, the (meth) acrylates thus obtainable are unstable under polymerization conditions in the presence of acids, for example acid group-carrying comonomers, and lead to inhibition of the polymerization by liberation of phenol and strongly colored product mixtures. EP 2762506 A1 discloses (meth) acryloyl-terminated polyisobutenyl polymers. The stated aim of EP 2762506 A1 is to prepare crosslinkable macromolecules, preferably with a functionality of 2 or 3. The macromolecules explicitly disclosed in the examples have a functionality of 1, 9 or higher. This causes crosslinking under polymerization conditions

Furthermore, the macromolecules disclosed therein are prepared by a cationic polymerization of appropriately functionalized starter molecules, and the resulting polyfunctionalized polyisobutene polymers bearing a chlorine atom at each chain end are coupled to a (meth) acryloyl-substituted phenol by Friedel-Crafts alkylation.

This method of production requires that the products have a marked content of chlorine due to their production, which is given in the examples as 79 to 85 ppm.

From EP 832960 A1 it is known to alkoxylate polyisobutenyl-substituted phenols with carbonates or alternatively with alkylene oxides.

As products, only monoalkoxylated products are described, but no multiple alkoxylated, in particular, is not discussed on the distribution of polyalkoxylated products according to this method. The object of the present invention was to provide uniformly monofunctional compounds with which a high proportion of structural units of polyisobutene-carrying phenols can be introduced into polymers. These compounds are said to be stable under polymerization conditions and more readily available than said compounds in the prior art and have a lower halogen content, as it is disclosed in the examples of EP 2762506 A1.

The object has been achieved by compounds (A) of the formula (I)

wherein R ¹ to R ⁵ are each independently selected from the group consisting of hydrogen, _{Ci-C2o-alkyl,} Ci-C ₂ o-alkyloxy and C ₈ -C ₃ 5oo-polyisobutyl and C ₈ -C ₃ 5oo- polyisobutenyl,

 R is an alkylene group having from 2 to 10, preferably from 2 to 6 and particularly preferably from 2 to 4, carbon atoms,

R ^{6 is} hydrogen or methyl,

R ^{7 is} hydrogen, methyl or COOR ⁸ ,

R ^{8 is} hydrogen or Ci-C ₂ o-alkyl and

n is a positive integer from 1 to 50

with the proviso that at least one of R ¹ to R ^{5 is} a Cs-Cssoo polyisobutyl or Cs-Cssoo polyisobutenyl.

A further subject of the invention are polymers comprising in copolymerized form at least one compound (A) of the formula (I)

R ¹ to R ^{5 are} each independently selected from the group consisting of hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 -alkyloxy and C 2 -C 8 -socoisobutyl and C 8 -C 3500 -polyisobutenyl,

 R is an alkylene group having from 2 to 10, preferably from 2 to 6 and particularly preferably from 2 to 4, carbon atoms,

R ^{6 is} hydrogen or methyl,

R ^{7 is} hydrogen, methyl or COOR ⁸ ,

R ^{8 is} hydrogen or CC ₂ o-alkyl and

n is a positive integer from 1 to 50

with the proviso that at least one of R ¹ to R ^{5 represents} a Cs-Cssoo polyisobutyl or Cs-Cssoo polyisobutenyl and optionally at least one monomer (B) selected from the group consisting of

(B1) other (meth) acrylates than (A), (B2) other fumaric and maleic acid derivatives than (A), (B3) alkyl vinyl ethers

(B4) styrene and α-methylstyrene (B5) acrylonitrile

(B6) Vinylalkanoates and (B7) (meth) acrylamides. Mean in it

C 1 -C 20 -alkyl, for example, methyl, ethyl, n-propyl, n-propyl, n-butyl, n-butyl, n-butyl and n-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2 Methylbutyl, 3-methylbutyl, 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl, n -hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl, 2-methylpent-3 - yl, 2-methylpent-2-yl, 2-methylpent-4-yl, 3-methylpent-2-yl, 3-methylpent-3-yl, 3-methylpentyl, 2,2-dimethylbutyl, 2,2-dimethylbut 3-yl, 2,3-dimethylbut-2-yl, 2, 3-dimethylbutyl, 2-ethylhexyl, n-octyl, 2-propylheptyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n Octadecyl and eicosyl, preferably methyl, ethyl, n-butyl, so-propyl, fe-butyl, 2-ethylhexyl and 2-propylheptyl and particularly preferably methyl, ethyl, n-butyl, / so-propyl or fe / 7-butyl, very particularly preferably methyl, ethyl or n-butyl, in particular methyl or ethyl, especially methyl.

C 1 -C 20 -alkyloxy, for example, oxygen radicals substituted by C 1 -C 20 -alkyl groups, preferably methoxy, ethoxy, / so-propyloxy, n-propyloxy, n-butyloxy, / so-butyloxy, secA ^" -butyloxy and tert-butyloxy, particularly preferably methoxy , Ethoxy, n-butyloxy, / so-propyloxy and fe / 7-butyloxy, and most preferably methoxy.

An alkylene group having 2 to 10 carbon atoms is 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 1-phenyl-1,2 -ethylene and 2-phenyl-1, 2-ethylene, preferably 1, 2-ethylene, 1, 2-propylene and 1, 2-butylene.

C8-C35oo-polyisobutyl and Cs-Cssoo-polyisobutenyl by addition of 8 to 3500 carbon atoms containing polyisobutene on aromatics available radicals.

The Cs-Cssoo polyisobutyl and Cs-Cssoo polyisobutenyl radicals may in principle be based on any conventional and commercially available polyisobutene which is introduced in a suitable manner into the synthesis of the compounds of the formula (I). Such a polyisobutene preferably has a number average molecular weight M _n of at least 200. Preference is given to polyisobutenes having a number average molecular weight M _n in the range of at least 500, more preferably of at least 700 and very particularly preferably of at least 900 g / mol.

It is possible to use polyisobutenes having a number average molecular weight M _n in the range of up to 50,000, preferably up to 45,000, more preferably up to 40,000, and most preferably up to 35,000 g / mol.

In a preferred embodiment, the number average molecular weight M _{n of} the polyisobutenes can be up to 30,000, more preferably up to 20,000 and most preferably up to 10,000 g / mol.

In a further preferred embodiment, the number average molecular weight M _{n of} the polyisobutenes can be from 700 to 2500 and more preferably from 900 to 1100 g / mol. For the purposes of the present invention, the term "polyisobutene" also includes oligomeric isobutenes, such as dimeric, trimeric, tetrameric, pentameric, hexameric and heptameric isobutene.

Preferably, the C8-C3500 polyisobutyl and Cs-Cssoo polyisobutenyl radicals incorporated in the compounds of the formula (I) are derived from so-called "highly reactive" polyisobutene. "Highly reactive" polyisobutenes differ from other polyisobutenes in the content of terminal double bonds. Thus, highly reactive polyisobutenes contain at least 50 mol% terminal double bonds, based on the total number on polyisobutene macromolecules. Particular preference is given to polyisobutenes having at least 60 mol% and in particular at least 80 mol% terminal double bonds, based on the total number of polyisobutene macromolecules. The terminal double bonds can be both vinyl double bonds [-CH = C (CH 3) 2] (β-olefin) and vinylidene double bonds [-CH-C (= CH 2) -CH 3] (α-olefin) , preferably olefins. In addition, the substantially homopolymeric polyisobutenyl radicals have uniform polymer skeletons. In the context of the present invention, these are understood as meaning polyisobutene systems which comprise at least 85% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight, of isobutene units of the repeat unit [-] CH ₂ C (CH ₃ ) 2-] are constructed.

In the present specification, a distinction is made between polyisobutyl and polyisobutenyl radicals, the polyisobutyl radicals being essentially free of double bonds and the polyisobutenyl radicals generally carrying at least one double bond per radical.

The Brönstedt or Lewis acid catalyzed addition of polyisobutene to aromatics usually proceeds under reaction of the double bond and therefore provides essentially double bond-free polyisobutyl. In this context, "essentially double bond-free" means that not more than 25% of all radicals carry one double bond, preferably not more than 15%, more preferably not more than 10% and very particularly preferably not more than 5%.

Polyisobutyl radicals are preferred over the polyisobutenyl radicals.

A further preferred feature of the polyisobutenes, which may be based on the compounds of the formula (I) according to the invention, is that they contain at least 15% by weight, in particular at least 50% by weight, especially at least 80% by weight. -% with a tert-butyl group [-CH ₂ C (CH ₃ ) 3] are terminated.

Furthermore, the polyisobutenes which preferably serve as the basis for the compounds of the formula (I) according to the invention preferably have a polydispersity index (PDI) of from 1.05 to 10, preferably from 1.05 to 3.0, in particular from 1.05 to 2.0 , Polydispersity is understood to mean the quotient of weight-average molecular weight M _w and number-average molecular weight M _n (PDI = M _w / M _n ).

For the purposes of the present invention, "polyisobutenes" which are preferably used as the basis for the compounds of the formula (I) according to the invention are also all polymers obtainable by cationic polymerization, which preferably contain at least 60% by weight of isobutene, more preferably at least 80% by weight. , Above all, at least 90 wt .-% and in particular at least 95 wt .-% of isobutene in copolymerized form. In addition, the polyisobutenes can contain further butene isomers, such as 1- or 2-butene, as well as various olefinically unsaturated monomers copolymerizable with isobutene under cationic polymerization conditions. Suitable isobutene feedstocks for the production of polyisobutenes that (I) can serve as base for the novel compounds of the formula, both isobutene itself and isobutenic C4-hydrocarbon streams, for example C4 raffinates, C are accordingly ₄ cuts from isobutene -Dehydrogenation, C ₄ Slices from Steam Crackers, FCC (Fluid Catalyzed Cracking) Crackers, provided they are substantially freed of 1,3-butadiene contained therein. Particularly suitable C ₄ -hydrocarbon streams generally contain less than 500 ppm, preferably less than 200 ppm of butadiene. When using C ₄ cuts as feedstock, the hydrocarbons other than isobutene play the role of an inert solvent.

As copolymerizable with isobutene monomers are vinyl aromatics such as styrene and α-methyl styrene, Ci-C ₄ alkylstyrenes such as 2-, 3- and 4-methylstyrene, and 4-tert-butylstyrene, Isoole- fine having 5 to 10 carbon atoms, 2-methylbutene-1, 2-methylpentene-1, 2-methyl-hexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1 into consideration.

Typical polyisobutenes which are based on the compounds of the formula (I) according to the invention are, for example, the Glissopa KD grades from BASF SE, Ludwigshafen, z. Glissopal 1000, Glissopal 1300 and Glissopal 2300, as well as the OppanoKD brands of BASF SE, e.g. Oppanol® B10, B12 and B15.

In the formula (I), the radicals have the following meanings:

R ¹ to R ⁵ are each independently selected from the group consisting of hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 -alkyloxy and Cs-CsOs-polyisobutyl and C 8 -C 3500 polyisobutenyl.

Those of radicals R ¹ to R ⁵ which are a polyisobutyl or polyisobutenyl, preferably a polyisobutyl radical, have at least 8, preferably at least 12, more preferably at least 16, very preferably at least 20 and in particular at least 35 carbon atoms.

In a preferred embodiment, they have at least 50 and more preferably at least 60 carbon atoms. In general, the polyisobutyl or polyisobutenyl radicals have up to 3500 carbon atoms, preferably up to 3200, particularly preferably up to 2200, very particularly preferably up to 1500 and in particular up to 750.

In a preferred embodiment, they have up to 200, more preferably up to 100 and especially up to 80 carbon atoms. The proviso that at least one of the radicals R ¹ to R ^{5 represents} one of said polyisobutyl or polyisobutenyl, preferably one, two or three, more preferably one or two and most preferably exactly one. Those radicals R ¹ to R ⁵ which are not one of the polyisobutyl or polyisobutyl radicals mentioned are preferably selected from the group consisting of hydrogen, methyl, isopropyl, tert-butyl, methoxy, tert-butyloxy, more preferably selected from the group consisting of hydrogen, methyl, tert-butyl, and most preferably they are hydrogen.

In a preferred embodiment, at least one of R ¹ , R ³ and R ^{5 is} a polyisobutyl or polyisobutenyl radical and the others are not, more preferably R ^{3 is} a polyisobutyl or polyisobutenyl radical and the others are not. R is an alkylene group having 2 to 10, preferably 2 to 6 and particularly preferably 2 to 4, carbon atoms, preferably 1, 2-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 2-butylene , 1, 4-butylene, 1-phenyl-1, 2-ethylene or 2-phenyl-1, 2-ethylene, more preferably from 1, 2-ethylene, 1, 2-propylene or 1, 2-butylene and very particularly preferably 1, 2-ethylene.

N is a positive integer from 1 to 50, preferably from 1 to 30, particularly preferably from 1 to 20, very particularly preferably from 1 to 10, in particular from 1 to 5 and especially around 1. R ⁶ is hydrogen or methyl, preferably methyl.

R ⁷ is hydrogen, methyl or COOR ⁸ , preferably hydrogen or COOR ⁸ and particularly preferably hydrogen. R ⁸ is hydrogen or C ₁ -C 20 -alkyl, preferably hydrogen, methyl, ethyl, n-butyl or 2-

Ethylhexyl, more preferably hydrogen or methyl and most preferably hydrogen.

It should be noted that the compounds of the formula (I) are reaction mixtures having a distribution of the product composition depending on the reaction conditions. Thus, the chain length of the polyisobutyl or Polyisobutenylreste a distribution around a statistical average is subject, as well as the substitution pattern of the polyisobutyl or Polyisobutenylreste on the aromatic ring and optionally the length of the chain - [- R-0-] _n -, which is also a statistical Mean n can be distributed. Thus, the value of n for each individual compound of the formula (I) assumes positive integer numbers, and may also assume non-integer values for the reaction mixture on a statistical average. In a preferred embodiment, the reaction mixture has an average functionality of α, β-unsaturated carbonyl functions, preferably of (meth) acrylate groups of not more than 1, 2, more preferably of not more than 1, 1, most preferably of not more than 1 , 05th

The average functionality is generally at least 0.8, preferably at least 0.9 and most preferably at least 0.95.

The degree of functionalization can be determined by means of quantitative 1 H NMR spectroscopy. In this case, the signals of the protons on the aromatic, which are usually easy to allocate and detectable, and which are not superimposed by other signals, and the signals of the protons of the polymerizable double bond are integrated and set in relation to one another.

The preparation of the compounds (A) can be carried out, for example, by reacting the free phenols of the formula

with alkylene oxides or alkylene carbonates of the formula

followed by a decarboxylation and subsequent esterification with (meth) acrylic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride or transesterification with

(Meth) acrylic acid esters, crotonic acid esters, fumaric acid esters or maleic esters.

The preparation of the free phenols is known from the cited prior art, for example WO 02/059237 or WO 14/90672 and the literature cited therein.

Whereas EP 2762506 A1 carries out cationic polymerization starting from chlorinated starter molecules and leads to polyisobutene polymers bearing a chlorine atom at each chain end, which are coupled to a phenol, it constitutes a preferred embodiment of the invention. form of the present invention, a double bond-carrying polyisobutene with a Lewis acid by Friedel-Crafts alkylation to bind to a phenol. Thus, according to the process, the compounds according to EP 2762506 A1 have a substantially higher halogen content than this preferred embodiment of the reaction of a polyisobutene carrying a double bond with phenol in the presence of a Lewis acid.

Preference is given in this way to reaction mixtures having a halogen content, preferably a fluorine content, of not more than 70 ppm by weight, more preferably not more than 50 ppm by weight, very preferably not more than 40 ppm by weight, in particular not more than 30 Gew.ppm and especially not more than 20 Gew.ppm. It is even possible to obtain reaction mixtures having a halogen content, preferably a fluorine content, of not more than 10 ppm by weight or even not more than 5 ppm by weight.

The alkoxylated products are generally prepared by reacting the free phenols with the particular epoxide in the desired stoichiometry in the presence of a catalyst, for example an alkali metal or alkaline earth metal hydroxide, oxide, carbonate or hydrogen carbonate, preferably an alkali metal hydroxide, particularly preferably of potassium hydroxide. Possible embodiments can be found in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, 1979, Thieme Verlag Stuttgart, Ed. Heinz Kropf, Volume 6/1 a, Part 1, pages 373 to 385. A preferred embodiment can be found in the WO 02/059237 A2, there especially from page 9, line 12 to page 10, line 21, which is hereby incorporated by reference into the present disclosure.

The preparation of the alkoxylated products can also be carried out with the aid of multimetal cyanide compounds, frequently also referred to as DMC catalysts, which have been known for a long time and have been described many times in the literature, for example in US Pat. No. 3,278,457 and in US Pat. No. 5,783,513.

The DMC catalysts are usually prepared by reacting a metal salt with a cyano metal tetallate compound. To improve the properties of the DMC catalysts, it is customary to add organic ligands during and / or after the reaction. A description of the preparation of DMC catalysts can be found, for example, in US-A 3,278,457.

Typical DMC catalysts have the following general formula:

M a [M ² (CN) b] d'fM jX _k .h (H ₂ 0) eL ^'zP wherein M ¹ is a metal ion selected from the group consisting of Zn ^2+, Fe ^2+, Fe ^3+, Co ²⁺ , Co ³⁺ , Ni ²⁺ , Mn ²⁺ , Sn ²⁺ , Sn ⁴⁺ , Pb ²⁺ , Al ³⁺ , Sr ²⁺ , Cr ³⁺ , Cd ²⁺ , Cu ²⁺ , La ³⁺ , Ce ³⁺ , Ce ⁴⁺ , Eu ³⁺ , Mg ²⁺ , Ti ⁴⁺ , Ag ⁺ , Rh ²⁺ , Ru ²⁺ , Ru ³⁺ , Pd ²⁺ M ^{2 is} a metal ion selected from the group containing Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Mn ²⁺ , Mn ³⁺ , Ni ²⁺ , Cr ²⁺ , Cr ³⁺ , Rh ³⁺ , Ru ²⁺ , lr ³⁺ and M ¹ and M ^{2 are} identical or different,

X is an anion selected from the group consisting of halide, hydroxide, sulfate, hydrogensulfate, carbonate, hydrogencarbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate or nitrite (NO2 ^") or a mixture of two or more of the above- anions or a mixture of one or more of the abovementioned anions with one of the uncharged species selected from CO, H ₂ O and NO,

Y is different from X anion selected from the group consisting of, halide, sulfate, hydrogen sulfate, disulfate, sulfite, sulfonate (= RS0 ₃ ^"with R = _{Ci-C2o-alkyl, C6-Ci2} aryl, C1 C20 alkylaryl), carbonate, bicarbonate, cyanide, thiocyanate, isocyanate, isothiocyanate, cyanate, carboxylate, oxalate, nitrate, nitrite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, borate, tetraborate, perchlorate, tetrafluoroborate, hexafluorophosphate, tetraphenylborate .

L is a water-miscible ligand selected from the group comprising alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, nitriles, and sulfides or mixtures thereof,

P is an organic additive selected from the group comprising polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether , Polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkylene glycol. lenimines, maleic acid and maleic anhydride copolymer, hydroxyethyl cellulose, polyacetates, ionic surfaces and surface-active compounds, bile acid or its salts, esters or amides, carboxylic esters of polyhydric alcohols and glycosides. and a, b, d, g, n, r, s, j, k, and t are integer or fractional numbers greater than zero,

e, f, h, and z are integers or fractions greater than or equal to zero, where a, b, d, g, n, j, k, and r and s and t are selected to ensure electroneutrality,

Mean hydrogen or an alkali or alkaline earth metal, as well as M ⁴ alkali metal ions or an ammonium ion (NH ₄ ⁺ ) or alkylammonium ion (R ₄ N ⁺ , R ₃ NH ⁺ , R ₂ NH ₂ ⁺ , RNH ₃ ⁺ with R = C ₁ -C 20 -alkyl).

In a particularly preferred embodiment of the invention, M ^{1 is} Zn ²⁺ and M ^{2 is} Co ³⁺ or Co ²⁺ .

The metals M ¹ and M ² are especially the same if they are cobalt, manganese or iron. In a preferred embodiment, the alkoxylation takes place such that the polyisobutene-carrying phenol with an alkylene oxide, preferably selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, styrene oxide and mixtures thereof, in the presence of strong bases, preferably alkali metal and alkaline earth metal salts of C 1 -C ₄ -alcohols, alkali metal hydroxides and alkaline earth metal hydroxides, Bronsted acids or Lewis acids, such as AlC, BF 3, etc. is reacted. Preference is given to alkali metal and alkaline earth metal salts of C 1 -C ₄ -alcohols, alkali metal hydroxides and alkaline earth metal hydroxides, more preferably sodium methoxide, potassium methoxide, potassium

tert.butanolate, sodium hydroxide and potassium hydroxide, most preferably potassium tert.butanolate and potassium hydroxide. The amount used of the catalysts is generally in a range of about 0.01 to 1 wt .-%, in particular 0.05 to 0.5 wt .-%, based on the total amount of the reactants.

The alkoxylation is preferably carried out at temperatures in the range of about 70 to 200 ° C, preferably about 100 to 160 ° C. The pressure is preferably between ambient pressure and 150 bar, in particular in the range of 3 to 30 bar. If desired, the alkylene oxide may be an inert gas admixture, e.g. From about 5 to 60%.

The reaction product can be prepared by customary methods known to those skilled in the art, such as. B. by outgassing volatile components in vacuo or by stripping with a gas inert under the conditions and, if appropriate, be worked up by filtration.

The catalyst may also be separated by treatment of the product with magnesium silicates (for example Ambosol®) followed by filtration.

The residues of the catalyst can remain in the product obtained, or be neutralized with an acid, preferably hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid, the salts subsequently being preferably removed by, for example, a wash or by ion exchange. Optionally, a partial neutralization can take place and the product can be used further without further separation of the salts. The reaction with alkylene carbonates, preferably 1, 2-ethylene carbonate, 1, 3-propylene carbonate and 1, 2-propylene carbonate, is usually carried out in a stoichiometry of 1 to 2 moles of carbonate: 1 mol of phenol, preferably 1, 05 - 1, 8 : 1, more preferably 1, 1-1, 7: 1, most preferably 1, 2-1, 5: 1 mol / mol. As catalysts for the reaction with alkylene carbonates, it is possible to use inorganic salts, tertiary amines, triphenylphosphine, lithium hydride and organic stannates. The inorganic salt preferably has at least one anion selected from the group consisting of carbonate (COs ^{2 "} ), oxide (O ² -), hydroxide (OH), bicarbonate (HCO ₃ -) _> phosphate (P0 ₄ ^3" ) hydrogen phosphate (HPO4 ^{2 "} ) and dihydrogen phosphate (H2PO4 ^" ). Preferred are oxide, hydroxide and phosphate or mixtures thereof, particularly preferred is phosphate. The inorganic salt preferably has at least one cation selected from the group consisting of alkali metals, alkaline earth metals, tetraalkylammonium, ammonium, cerium, iron, manganese, chromium, molybdenum, cobalt, nickel or zinc. Preference is given to alkali metals and alkaline earth metals, and particular preference to lithium, sodium, potassium or calcium. Particularly preferred inorganic salts including their hydrates are LiOH, L13PO4, Na3PO4, K3PO4, Na2CO3, K2CO3 and CaO, most preferably K3PO4.

Conceivable, although less preferred are tetraalkylammonium halides, preferably tetra-C 1 -C 20 -alkyl ammonium halides and particularly preferably tetra-C 1 -C 4 -alkyl ammonium halides, among the halides preferably chlorides, bromides and iodide, more preferably chlorides or bromides, and all particularly preferably chlorides, and preferably tertiary amines such as Triethylamine and 2-methylimidazole most preferably 2-methylimidazole.

It may be advantageous to leave the catalyst in the reaction mixture after completion of the reaction and to use it in the subsequent reaction, see below. However, it is also possible to remove the catalyst from the reaction mixture, for example by an aqueous extraction of the reaction mixture or by filtration. For example, the laundry may be placed in a stirred tank or other conventional apparatus, e.g. be carried out in a column or mixer-settler apparatus. In terms of process technology, all the extraction and washing processes and apparatuses known per se can be used for a wash in the process according to the invention, e.g. those which are described in Ullmann's Encyclopedia of Industrial Chemistry, 6th ed., 1999 Electronic Release, Chapter "Liquid-Liquid Extraction - Apparatus." For example, these may be single-stage or multistage, preferably single-stage extractions and extractions in cocurrent or countercurrent running be.

A separation from the heterogeneous catalyst is usually carried out by filtration,

Electrofiltration, absorption, centrifugation or decantation, preferably by filtration. The separated heterogeneous catalyst can then be used for further reactions

be used.

The filtration can be carried out for example with a pressure suction filter. Technically, all known per se for filtration in the process according to the invention Filtration methods and apparatus are used, for example, those in Ullmann's Encyclopedia of Industrial Chemistry, 7th ed, 2013 Electronic Release, Chapter: Filtration, 1. Fundamentals and filtration 2. Equipment, are described. For example, these may be candle filters, filter presses, plate pressure filters, bag filters or drum filters. Preferably, candle filters or plate pressure filters are used.

The filtration can be carried out with or without filter aid. Suitable filter aids are filter aids based on kieselguhr, perlite and cellulose. Suitable centrifuges and separators are known to the expert. Technically, centrifugation in the process according to the invention can be carried out using all known centrifugation methods and apparatus, e.g. those described in Ullmann's Encyclopedia of Industrial Chemistry, 7th ed, 2013 Electronic Release, Chapter: Centrifuges, Filtering and Centrifuges, Sedimenting.

The reaction is generally carried out at a temperature of 70 to 200 ° C, especially at 100 to 190 and most preferably 150 to 170 ° C.

It is also possible to increase the reaction temperature in the course of the reaction in order to accelerate the decarboxylation after ring opening of the carbonate.

The reaction is usually completed within 24 hours, preferably within 1 to 20 hours, more preferably in 2 to 16 hours, most preferably 3 to 12 hours.

The reaction can be carried out without solvent or in the presence of such, for example ethers, ketones or hydrocarbons, preferably without solvent.

Among the hydrocarbons, the aromatic solvents having a boiling range at the particular pressure above the reaction temperature are preferred. Examples of these are those which comprise predominantly aromatic C ₇ - to C ₆ -hydrocarbons and may comprise a boiling range from 1 10 to 300 ° C., particular preference is given to toluene, o-, m- or p-xylene, trimethylbenzene isomers, tetramethylbenzene isomers, Ethylbenzene, cumene, tetrahydronaphthalene and mixtures containing same. Further examples are the Solvesso® grades from ExxonMobil Chemical, in particular Solvesso® 100 (CAS No. 64742-95-6, predominantly Cg and Cio-aromatics, boiling range about 154-178 ° C.), 150 (boiling range approx 182-207 ° C) and 200 (CAS No. 64742-94-5), as well as the Shellsol® brands from Shell, Caromax® (eg Caromax® 18) from Petrochem Carless and Hydrosol from DHC (eg as Hydrosol® A 170). Hydrocarbon mixtures of paraffins, cyclopa raffins and aromatics are also called crystal oil

(for example, crystal oil 30, boiling range about 158-198 ° C. or crystal oil 60: CAS No. 64742-82-1), white spirit (for example also CAS No. 64742-82-1) or solvent naphtha (light: boiling range about 155 ° C.) 180 ° C, heavy: boiling range about 225-300 ° C) commercially available borrowed. The aromatic content of such hydrocarbon mixtures is generally more than 90% by weight, preferably more than 95, more preferably more than 98, and very preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.

It is a preferred embodiment of the present invention to first react the free phenol with a carbonate, preferably ethylene carbonate, and then reacting the thus obtainable, a group -ROH-carrying reaction product with an alkylene oxide or alkylene oxide mixture until the desired number n in the Structural unit - [- R-0-] _n - is reached.

This has the advantage that a narrower molecular weight distribution is obtained.

Another advantage is that such products are available in which - in the structural unit - [- R-0-] _n - the first structural unit - [- RO -] - of the second to nth structural unit - [- RO -] - can distinguish.

The esterification with (meth) acrylic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride or transesterification with (meth) acrylic acid esters, crotonic acid esters, fumaric acid esters or maleic acid esters of the alkoxylated phenol of the formula

is usually done as follows:

For this purpose, the alkoxylated phenol and (meth) acrylic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride in a molar ratio of acid to phenol of usually at least 1: 1, preferably at least 1, 05: 1, particularly preferably at least 1, 1: 1, most preferably at least 1, 25: 1 and in particular at least 1, 5: 1 reacted. In general, a molar ratio of not more than 5: 1 is required, preferably not more than 4: 1, more preferably not more than 3: 1 and most preferably not more than 2: 1.

Useful esterification catalysts are sulfuric acid, aryl or alkylsulfonic acids or mixtures thereof. Examples of arylsulfonic acids are benzenesulfonic acid, para-

Toluene sulfonic acid or dodecyl benzene sulfonic acid, examples of alkyl sulfonic acids are methanesulfonic acid, ethanesulfonic acid or trifluoromethanesulfonic acid. Also very acidic shear or zeolites can be used as esterification catalysts. Preference is given to sulfuric acid and sulfonic acids, more preferably methanesulfonic acid and para-toluenesulfonic acid.

These are generally used in an amount of 0.1-5% by weight, based on the esterification mixture, preferably 0.5-5, more preferably 1-4 and very particularly preferably 2-4% by weight. %.

If necessary, the esterification catalyst can be removed from the reaction mixture by means of an ion exchanger. The ion exchanger can be added directly to the reaction mixture and then filtered off, or the reaction mixture can be passed through a ion exchanger bed.

Preferably, the esterification catalyst is left in the reaction mixture. If, however, the catalyst is an ion exchanger, it is preferably removed, for example by filtration.

The esterification or transesterification is preferably added to a polymerization inhibitor known per se in a total amount of 0.01-5% by weight, based on the esterification mixture, preferably 0.02-3, particularly preferably 0.05-2% by weight. %, very particularly preferably 0.1 to 1 and in particular 0.3 to 1 wt .-%.

Examples of such polymerization inhibitors are listed, for example, in WO 2005/082828 A1, there in particular from page 15, line 27 to page 19, line 18, which is hereby incorporated by reference in the present disclosure.

For the effectiveness of the polymerization inhibitors, it may be advantageous to pass an oxygen-containing gas, for example air or lean air, over or preferably through the reaction mixture. The water of reaction formed in the reaction may be distilled off during or after the esterification, which process may be assisted by a solvent forming an azeotrope with water.

As a solvent for azeotropic removal of the water of reaction, if desired, especially aliphatic, cycloaliphatic and aromatic hydrocarbons or mixtures thereof are suitable.

Preference is given to using n-pentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, benzene, toluene or xylene. Particularly preferred are cyclohexane, methylcyclohexane and toluene.

Preference is given to carrying out the esterification in the presence of a solvent. The amount of solvent used is 10 to 200% by weight, preferably 20 to 100% by weight, more preferably 30 to 100% by weight, based on the sum of phenol and acid. If the water contained in the reaction mixture is not removed via an azeotroping solvent, it is possible to remove it by stripping with an inert gas, preferably an oxygen-containing gas, more preferably air or lean air.

The reaction temperature of the esterification is generally 40-160 ° C, preferably 60-140 ° C and more preferably 80-120 ° C. The temperature can remain constant or increase in the course of the reaction, preferably it is raised in the course of the reaction. In this case, the final esterification temperature is 5 - 30 ° C higher than the initial temperature.

If a solvent is used, it can be distilled off from the reaction mixture after completion of the reaction.

The reaction mixture is optionally in a washing apparatus with water or a 5-30 wt .-%, preferably 5-20, more preferably 5-15 wt .-% sodium chloride, potassium chloride, ammonium chloride, sodium sulfate or aluminum sulfate solution is preferred Saline treatment.

The quantitative ratio of reaction mixture: washing liquid is generally 1: 0.1-1, preferably 1: 0.2-0.8, particularly preferably 1: 0.3-0.7. The laundry may, for example, in a stirred tank or in another conventional apparatus, for. B. in a column or mixer-settler apparatus are performed,

Technically, all the known extraction and washing methods and apparatus can be used for a wash in the process of the invention, for. For example, those described in Ullmann's Encyclopedia of Industrial Chemistry, 6th ed, 1999 Electronic Release, Chapter: Liquid - Liquid Extraction - Apparatus. For example, these may be single-stage or multistage, preferably single-stage extractions, as well as those in cocurrent or countercurrent mode.

Prewash is preferably used when metal salts, preferably copper or copper salts, are used as inhibitors.

The organic phase of the prewash, which still contains small amounts of catalyst and the majority of excess (meth) acrylic acid, is treated with a 5-25, preferably 5-20, more preferably 5-15 wt .-% aqueous solution of a base, such as z. For example, sodium hydroxide solution, potash, sodium bicarbonate, sodium carbonate, potassium bicarbonate, calcium hydroxide, ammonia or potassium carbonate, which may optionally be added 5-15 wt .-% sodium chloride, potassium chloride, ammonium chloride or ammonium sulfate, preferably neutralized with sodium hydroxide or sodium chloride-sodium chloride solution , The addition of the base is carried out in such a way that the temperature in the apparatus does not rise above 35 ° C, preferably between 20 and 35 ° C and the pH is 10-14. The heat of neutralization is optionally removed by cooling the container by means of internal cooling coils or by double-wall cooling.

 The quantitative ratio reaction mixture: neutralizing liquid is generally 1: 0.1-1, preferably 1: 0.2-0.8, particularly preferably 1: 0.3-0.7.

With regard to the apparatus, the above applies.

Optionally, to remove base or salt traces from the neutralized reaction mixture, a post-wash may be advantageous, which may be carried out analogously to the prewashing. Alternatively, the reaction mixture can be worked up by adding a 20-50% aqueous sodium hydroxide solution, preferably 25-35%, particularly preferably 30%, and then adding a mineral, water-absorbing substance and filtration, whereby the excess acid and the catalyst are separated off. For example, montmorillonite-containing phyllosilicates, such as bentonite or aluminosilicates (Ambosol®), can be used.

In a further embodiment, the esterification by reaction of the alcohol with (meth) acrylic anhydride can preferably be carried out in the presence of at least one basic catalyst. Preference is given to those catalysts which have a pK _B value of not more than 110, preferably not more than 7.0, and more preferably not more than 3.0.

In principle, all bases such as alkali and alkaline earth metal hydroxides and inorganic salts are suitable. Alkali and alkaline earth metal hydroxides can be dissolved both solid and in solvents, for example as aqueous solutions.

The inorganic salt preferably has at least one anion selected from the group consisting of carbonate (C0 ₃ ² -), oxide (O ² -), hydroxide (OH), bicarbonate (HCO ₃ -) _> phosphate (P0 ₄ ^{3 "} ) oxide, hydroxide and phosphate or mixtures thereof are preferred hydrogen phosphate (HPO4 ^{2 ")} and dihydrogen phosphate ^(H2PO4")., more preferably phosphate. the inorganic salt preferably has at least one, cation selected from the group consisting of alkali metals, alkaline earth, tetraalkylammonium, Ammonium, cerium, iron, manganese, chromium, molybdenum, cobalt, nickel or zinc, alkali metals and alkaline earth metals are preferred, and lithium, sodium, potassium or calcium are particularly preferred. L13PO4, Na3PO4,

K ₃ PO 4, Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ and CaO, most preferably NaOH, K ₂ C0 ₃ and K3PO4. In an alternative embodiment, the preparation of the compound of the formula (I) can also be effected by transesterification instead of esterification. For this purpose, preference is given to using a C 1 -C 4 -alkyl ester of the acid instead of a free acid, ie a methyl, ethyl, n-propyl, isophoryl, n-butyl, sec-butyl, isobutyl or tert. Butyl ester, preferably a methyl, ethyl or n-butyl ester, more preferably a methyl or ethyl ester, and most preferably a methyl ester.

As catalysts for the preparation of (meth) acrylsäureestern by transesterification can be employed, for example, titanium alcoholates whose alkyl Ci - C ₄ - alkyl radicals, (for example tetramethyl, tetraethyl, tetraisopropyl, tetrapropyl, tetrabutyl and Tetraisobutyl- see, for example EP B1 298 867, EP-A2 960 877). Furthermore, as catalysts include titanium phenolates (DE-OS 200 86 18), metal chelate compounds of z. As hafnium, titanium, zirconium or calcium, alkali metal and magnesium, organic tin compounds such as dimethyltin oxide, dibutyltin oxide or diphenyltin oxide, or inorganic salts proposed.

Other suitable tin-containing catalysts are Sn (IV) containing compounds such. Dialkyltin dichloride, dialkyltin oxide, dialkyltin diacetate, bis (trialkyltin) oxide, bis (dibutylchlorotin) oxide, for example dibutyltin dichloride, dimethyltin dichloride and dibutyltin oxide. The chloride-containing catalysts can be used together with alcoholates, for example with sodium methylate.

The inorganic salt preferably has at least one anion selected from the group consisting of carbonate (COs ^{2 "} ), oxide (O ² -), hydroxide (OH), bicarbonate (HCO ₃ -) _> phosphate (P0 ₄ ^3_ ) Hydrogen phosphate (HP0 ₄ ^2_ ) and dihydrogen phosphate (H ₂ P0 ₄ ^" ). Preferred are oxide, hydroxide and phosphate or mixtures thereof, particularly preferred is phosphate. The inorganic salt preferably has at least one cation selected from the group consisting of alkali metals, alkaline earth metals, tetraalkylammonium, ammonium, cerium, iron, manganese, chromium, molybdenum, cobalt, nickel or zinc. Preference is given to alkali metals and alkaline earth metals and particular preference to lithium, sodium, potassium or calcium. Particularly preferred inorganic salts including their hydrates are LiOH, L13PO4, Na3P0 _4, K3PO4, Na2C03, K2CO3 and CaO, very particularly preferably K3PO4.

Particularly suitable are heterogeneous catalysts or homogeneous catalysts which can be converted into heterogeneous residues as described in the transesterification processes, for example in DE 2 317 226 A1, DE 10 2004 036 930 A1 and WO2009 / 080380. The catalysts or residues of the catalysts are usually separated by filtration, electrofiltration, absorption, centrifugation or decantation. For the preparation of the compounds of the formula (I), it is possible to use all transesterification catalysts described in the prior art, preferably inorganic salts including their hydrates: LiOH, Li ₃ PO ₄ , Na ₃ PO ₄ , K ₃ PO ₄ , Na ₂ CO ₃ , K ₂ CO ₃ and CaO. The transesterification reaction is generally carried out at a temperature of 60 to 140 ° C, preferably 70 to 1 10 ° C. In this case, an azeotrope of entrainer and alcohol is distilled off continuously. Suitable entraining agents which form an azeotropically boiling mixture with C 1 -C 4 -alcohols are first the corresponding C 1 -C 4 -alkyl esters themselves. Suitable separate entraining agents include cyclohexane, methylcyclohexane, benzene, toluene, hexanes and heptanes and mixtures thereof. Preferred are methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate and mixtures of these with n-heptane and cyclohexane. The term entraining agent in this sense comprises the starting material itself and, if appropriate, an additionally used separate solvent.

In a preferred embodiment, no separate solvent is used as entraining agent. In this case, the reactant alkyl (meth) acrylate itself acts as an entraining agent.

The entrainer can then be replenished in the reactor. For this purpose, the azeotropic mixture of alcohol and entraining agent is distilled off in a preferred embodiment via a suitable column, stirred with water in a mixing vessel and then transferred to a phase sense separator, the alcohol, generally methanol or ethanol, dissolving in water and the organic phase separates as the upper layer. The organic phase is preferably fed back to the reaction mixture via the top of the column and thus recirculated to low losses. However, it is also possible to add fresh entraining agent as an alternative and to work up the entrainer-alcohol mixture in a separate step or to omit the addition of the entrainer entirely or partially.

In general, alkyl (meth) acrylate is used in stoichiometric excess. Preferably, the excess of methyl (meth) acrylate per hydroxyl group to be esterified is 0.1 to 100 equivalents, more preferably 3 to 50 equivalents, especially 10 to 40 equivalents.

The catalyst is used in a concentration of 2-20 mol% based on the amount of alcohol, preferably in a concentration of 3 to 10 mol%. The transesterification can be carried out at atmospheric pressure, but also at overpressure or underpressure. In general, it is carried out at 300 to 1000 mbar, preferably at 800-1000 mbar (atmospheric pressure = 1000 mbar). The reaction time is generally 1 hour to 24 hours, preferably 3 to 18 hours, more preferably 6 to 12 hours. The transesterification can be carried out continuously, for example in a stirred tank cascade or discontinuously. The reaction can be carried out in all reactors suitable for such a reaction. Such reactors are known to the person skilled in the art. The reaction preferably takes place in a stirred tank reactor. For mixing the batch can be used any method such as stirring devices. The mixing can also be done by feeding a gas, preferably an oxygen-containing gas.

The removal of the alcohol formed, generally methanol or ethanol, takes place continuously or stepwise in a manner known per se by azeotropic distillation in the presence of an entraining agent. In addition, methanol can also be removed by stripping with a gas.

In a preferred embodiment, the alcohol is separated off by washing with water from the distilled-off azeotrope of entrainer and alcohol, and the entraining agent is returned to the reaction vessel.

After completion of the reaction, the catalyst can be removed from the product by the separation processes or filtration already described, and the entrainer can be distilled off.

It is a preferred embodiment of the present invention, between the reaction of the free phenol with carbonate and / or alkylene oxide and the esterification or transesterification, no Aufarbeitgsschritt, such as extraction or filtration to perform.

It represents a further preferred embodiment of the present invention, for the reaction of the free phenol with carbonate and / or alkylene oxide and the esterification or transesterification, particularly preferably for the reaction of the free phenol with carbonate and subsequent transesterification or reaction with (meth) acrylic anhydride to use the same catalyst.

This is advantageous in particular when the catalysts used for the reaction of the free phenol with carbonate and / or alkylene oxide and the catalysts of esterification or transesterification interact negatively with one another, for example acids and bases.

It is advantageous, the reaction of the free phenol with the carbonate under catalysis of a tetraalkylammonium halide, EDTA or a tert. Amines such as triethylamine, 2-methylimidazole and the transesterification as described above in more detail perform. It is likewise advantageous to carry out the reaction of the free phenol with the carbonate with catalysis of a tetraalkylammonium halide or EDTA and the esterification in the presence of an acid as described in more detail above. It is also advantageous, the reaction of the free phenol with the carbonate under catalysis of a tetraalkylammonium halide, EDTA or a tert. Amines such as triethylamine, 2-methylimidazole and the esterification with (meth) acrylic anhydride as described in more detail above.

It is particularly advantageous to carry out both the reaction of the free phenol with the carbonate and the transesterification or the esterification with (meth) acrylic anhydride with catalysis of an inorganic salt as described in more detail above. A particular advantage here is the simple separation of the catalyst via a filtration after carrying out the two reaction steps.

It is equally advantageous to carry out both the reaction of the free phenol with the carbonate and the transesterification with catalysis of the following catalysts:

Alkali, alkaline earth, tetraalkylammonium halides, hydroxides, oxides, carbonates, bicarbonates or phosphates

An advantage of this procedure is that in this case it is possible to dispense with the removal of the catalyst from the alkoxylated phenol, but this can only take place at the stage of the compound of the formula (I).

Another object of the present invention are polymers containing at least one compound (A) in copolymerized form. In a preferred embodiment, these polymers may be homopolymers containing exclusively compounds of the formula (I) in copolymerized form, or in another equally preferred embodiment, copolymers which, in addition to at least one compound of the formula (I), also have at least one other monomer (B) selected from the group consisting of

(B1) other (meth) acrylates than (A), (B2) fumaric and maleic acid derivatives, (B3) alkyl vinyl ethers

(B4) styrene and α-methylstyrene (B5) acrylonitrile

(B6) vinyl alkanoates and (B7) (meth) acrylamides.

The monomers (B1) are acrylic acid, methacrylic acid and others

(Meth) acrylates as (A), preferably acrylic acid, methacrylic acid, cycloalkyl (meth) acrylates, alkyl (meth) acrylates and (meth) acrylates of polyalkylene glycol monoethers.

Preferred cycloalkyl (meth) acrylates are cycloalkyl (meth) acrylates whose cycloalkyl radical is formed from a three- to twelve-membered ring, preferably a five- to twelve-membered ring, and more preferably a five- or six-membered ring.

Particularly preferred are cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate and cyclododecyl (meth) acrylate, particularly preferably cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate and cyclododecyl (meth) acrylate , very particularly preferably cyclopentyl (meth) acrylate and cyclohexyl (meth) acrylate and in particular cyclohexyl (meth) acrylate, the acrylates in each case being preferred over the methacrylates.

Examples of alkyl (meth) acrylates are alkyl (meth) acrylates whose alkyl radical comprises one to 20 carbon atoms, preferably one to 12 and particularly preferably one to 8. In particular, methyl (meth) acrylate, ethyl (meth) acrylate, iso Propyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl ( meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate, n-heptadecyl (meth) acrylate), n-octadecyl (meth) acrylate, n-eicosyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and 2-propylheptyl (meth) acrylate, particularly preferred are methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, very particularly preferred are methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate and 2-ethylhexyl acrylate, and most preferably n Butyl acrylate and 2-ethylhexyl acrylate.

Examples of (meth) acrylates of oligo- and polyalkylene glycol monoethers are (meth) acrylates of oligo- and polyethylene glycol monoalkyl ethers, preferably the phenyl ethers, methyl ethers or n-butyl ethers, more preferably the methyl ethers or n-butyl ethers, and most preferably the methyl ethers. Fumaric and maleic acid derivatives (B2) include fumaric and maleic acid and the C 1 to C ₄ alkyl esters and, in the case of maleic acid, the maleic anhydride. Fumaric and maleic acid, fumaric and maleic acid methyl, ethyl, n-butyl and 2-ethylhexyl esters and maleic anhydride are preferred, maleic anhydride being particularly preferred. The alkyl vinyl ethers (B3) may preferably be alkyl vinyl ethers, preferably C 1 -C 8 -alkyl vinyl ethers, more preferably selected from the group consisting of methyl vinyl ether, ethyl vinyl ether, / 7-propyl vinyl ether, / so-propyl vinyl ether, / 7- Butyl vinyl ether, sec. Butyl vinyl ether, / so-butyl vinyl ether, Fe / 7-butyl vinyl ether, hexyl vinyl ether and octyl vinyl ether, and mixtures thereof.

As monomer (B4), mention may be made of styrene and α-methylstyrene, preferably styrene.

The monomer (B5) is acrylonitrile.

The vinyl alkanoates (B6) are preferably vinyl esters of 2 to 13 carbon atoms, preferably selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate and vinyl neodecanoate preferably selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl neopentanoate, very particularly preferred is vinyl acetate. The monomer (B7) is preferably methacrylamide and acrylamide, more preferably acrylamide.

Preference is given here to the monomers (B1), (B3), (B4) and (B7), particularly preferably (B1) and (B3) and very particularly preferably (B1).

It may be sufficient if the proportion of the monomer (A) in the copolymerized form in the polymer is at least 1% by weight, preferably at least 2% by weight, more preferably at least 5% by weight and most preferably at least 8% by weight. Preferably, the proportion of monomer (A) in polymerized form should be at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight and most preferably at least 50% by weight.

The proportion of monomer (A) in polymerized form can be up to 100% by weight (homopolymer), preferably up to 95% by weight, more preferably up to 90%, very preferably up to 85% and especially up to 70% by weight.

In the case of copolymers, one or more than one monomer other than (A) may be used, preferably one, two or three, more preferably one or two and most preferably exactly one.

It is possible to polymerize the monomer components (A) and optionally (B) preferably substance, in suspension or in solution, more preferably in solution or suspension, most preferably in emulsion. For this purpose, the polymerization reaction is generally carried out under normal pressure and under an inert gas such as nitrogen, but it can also operate at elevated pressures, for example in an autoclave. The polymerization temperatures are generally from 50 to 250 ° C, especially at 90 to 210 ° C, especially at 120 to 180 ° C, typically at 140 to 160 ° C. As a polymerization reactor, in principle, all customary continuous Continuously or discontinuously operated equipment such as stirred tank, stirred tank cascade, tubular reactor or loop reactor.

In the case of emulsion polymerization, the polymerization is preferably carried out without applying external pressure at temperatures of 50 to 95 ° C.

Usually, the polymerization is initiated by radically decomposing initiators, suitable for this purpose are air or oxygen or inorganic or organic peroxides and / or hydroperoxides and organic azo compounds. Examples of organic peroxides or hydroperoxides are diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide,

 Cumene hydroperoxide, methyl isobutyl ketone peroxide, di-tert-butyl peroxide and tert-butyl perisononate. As the organic azo compound, for example, azobisisobutyronitrile ("AIBN") is suitable. In addition to peroxodisulfates to mention in addition to hydrogen peroxide, especially sodium peroxodisulfates.

Also conceivable are redox pairs of the above peroxides or hydroperoxides with disulfites, the adduct of a disulfite and acetone, preferably acetone bisulfite or Rongalit® C.

Furthermore, suitable regulators such as aliphatic aldehydes or ketones or hydrogen can also be used in the polymerization.

If solvents or suspending agents are used in the polymerization, the customary inert liquids such as aromatic hydrocarbons, eg. As toluene, xylene or corresponding technical hydrocarbon mixtures such as Solvesso® or Solvent Naphtha, and aliphatic and cycloaliphatic hydrocarbons and hydrocarbon mixtures, such as pentane, hexanes, heptanes, petroleum ether, ligroin, cyclohexane, methylcyclohexane and decalin, into consideration.

In a preferred embodiment, the polymerization is carried out by means of emulsion polymerization, more preferably by means of miniemulsion polymerization.

In a preferred embodiment, it is carried out by means of miniemulsion polymerization as in WO 2016/046195 A1, there especially from page 15, line 31 to page 27, line 32, which is hereby incorporated by reference into the present disclosure.

In these processes, a mixture is generally prepared in a first step from the monomers, the necessary amount of emulsifier and / or protective colloid, optionally hydrophobic additive and water, and an emulsion is produced therefrom. The hydrophobic monomers are pre-emulsified by the auxiliaries.

In a first step, the organic phase is preferably prepared homogeneously and in a second step this organic phase is added to a water phase or a water phase is added to the organic phase thus prepared. Subsequently, an oil-in-water macroemulsion is prepared by stirring. The particles of the macroemulsion are comminuted by ultrasound and / or high-pressure homogenization to a size of less than 1 μm.

In the emulsion thus prepared, the average particle size (z average), measured by means of dynamic light scattering, is generally <1000 nm, preferably <500 nm and particularly preferably 20-500 nm. In the normal case, the diameter is 50-400 nm obtained particles decide in comparison to the classical emulsion polymerization in size. While in the classical emulsion polymerization, the droplet size is greater than 1, 5 μηη, especially 2 to 50 μηη, so is the droplet size in the preparation of a miniemulsion less than 1000 nm. The emulsified in droplet form present monomers are then polymerized by an initiator.

To produce the emulsion, an energy input of not more than 10 ⁸ W / m ^{3 is} required according to the invention.

It is expedient to carry out the preparation of the emulsion so rapidly that the emulsification time is small in comparison to the reaction time of the monomers with one another.

A preferred embodiment of the process consists in preparing the total amount of the emulsion with cooling to temperatures below room temperature. Preferably, the emulsion preparation is accomplished in less than 10 minutes. By increasing the temperature of the emulsion with stirring, the conversion is completed. The reaction temperatures are between room temperature and 120 ^° C, preferably between 60 ^° and 100 ^° C. If necessary, pressure can be applied to keep low-boiling components liquid.

In general, ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds in the production of emulsions.

A detailed description of suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, p. 41 1 to 420. Suitable emulsifiers are anionic, cationic and nonionic emulsifiers into consideration. Preferably used as accompanying surface-active substances are exclusively emulsifiers whose molecular weights, in contrast to the protective colloids, are usually below 2000 g / mol. Of course, in the case of the use of mixtures of surfactants, the individual components must be compatible with each other, which can be checked in case of doubt based on fewer, simple preliminary tests. Preferably, anionic and nonionic emulsifiers are used as surface-active substances. Common accompanying emulsifiers are, for example, ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: Cs to C36), ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ to Cg), alkali metal salts of dialkyl esters of sulfosuccinic acid and alkali metal and / or ammonium salts of alkyl sulfates (alkyl radical: Cs-C12), of ethoxylated alkanols (EO degree: 4 to 30, Cg), of alkylsulfonic acids (alkyl radical: C12-bis) Cis) and alkylarsulfonic acids (alkyl: Cg to Cis).

Suitable emulsifiers can also be found in Houben-Weyl, Methods of Organic Chemistry Volume 14/1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208. Trade names of emulsifiers are e.g. Dowfax® 2 A1 from Dow, Emulan® NP 50, Emulan® OG, Disponil® FES 27, Disponil® FES 32, Disponil® FES 77, Lutensol® AT 1 1, Disponil® SDS, Lutensol® AT 18, Lutensol Lutensol® TO 8, Lutensol TO® 10, Nekanil® 904 S from BASF, Lumiten® 1-RA and Lumiten E 3065 from BASF, Dextrol® OC 50 from Company AVEBE GmbH, etc.

Based on the amount of monomers contained in the aqueous emulsion, this amount of emulsifier is usually in the range of 0.1 to 10 wt .-%. As already mentioned, the emulsifiers can be given protective colloids which are able to stabilize the disperse distribution of the finally resulting aqueous polymer dispersion. Regardless of the amount of emulsifier used, the protective colloids can be used in amounts of up to 50% by weight, for example in amounts of from 1 to 30% by weight, based on the monomers.

As costabilizers as hydrophobic additive, the monomers may be added in amounts of from 0.01% by weight to 10% by weight, preferably 0.1-1% by weight, of substances having a solubility in water of less than 5 × ¹⁰ -5 , preferably 5 x I O- have ⁷ g / l. Examples are hydrocarbons such as hexadecane, halogenated hydrocarbons, silanes, siloxanes, hydrophobic oils (olive oil), dyes, etc. In their place, blocked polyisocyanates can also assume the function of hydrophobicity.

In a preferred embodiment, first a mixture of the monomers, emulsifiers and / or protective colloids, and optionally hydrophobic additive and water is prepared. Then an emulsion is produced and heated with stirring. After reaching the required reaction temperature, the initiator is added via the water phase. Of course, however, the initiator may already be in the oil phase of the emulsion, d. H. in the monomer phase, before being dispersed or added to the water phase immediately after preparation of the emulsion. The mixture is then heated with stirring and polymerized. The process for preparing a dispersion by miniemulsion polymerization can be described with particular preference as follows:

i. Mixing the monomers and possibly adding a cosolvent Preparation of a macroemulsion by the addition of the hydrophobic phase

Step i. in a premixed water emulsifier solution

 III crushing of the particles by ultrasound and / or high-pressure homogenization

Particle sizes less than 1000 nm, preferably <500 nm and particularly preferably 20

- 500 nm

 iv. Initiation of a free, radical polymerization of the oil-in-water miniemulsion from step iii.

The mass average molecular weight _Mw of the thus obtainable polymers is generally 5000 g / mol or more, preferably at least 10,000 g / mol, particularly preferably at least 20000 g / mol, very particularly preferably at least 30000 g / mol and in particular at least 50000 g / mol , And especially at least 100,000 g / mol.

The upper limit of the weight-average molecular weight Mw of the polymers thus obtainable is generally up to 1,000,000 g / mol, preferably up to 700,000 and more preferably up to 300,000 g / mol.

The polydispersity M _w / M _n is generally not more than 5, preferably not more than 4, more preferably not more than 3, very preferably not more than 2, and in particular not more than 1.5.

It is a particular advantage of miniemulsion polymerization that this compares with e.g. Solution or bulk polymerization higher molecular weights can be achieved. The compounds (A) obtainable according to the present invention and polymers containing them in polymerized form are used in the production of adhesives, adhesive raw materials, fuel additives, lubricant additives, as elastomers or as a basic constituent of sealing and sealing compounds.

Examples

Analysis Size exclusion chromatography was performed in THF + 0.1% trifluoroacetic acid at 35 ° C and a flow rate of 1 mL / min with a column combination of a possibly PLgel precolumn and two PLgel MIXED-B columns (iD 7.5 mm, length 30 cm, Exclusion limit 500- 10,000,000 g / mol). The calibration was done with narrow polystyrene standards. Example A

1775 g of polyisobutene (M _n 1000 g / mol) were dissolved in 360 g of hexane. 345 g of phenol were placed in 180 g of toluene in a 4L HWS vessel with bottom outlet and by means of a cooling thermostat cooled to 16 ° C. 32.7 g of BF ₃ -phenol complex was added to the phenol solution. The polyisobutene solution was added at 16 ° C. within 5 h 30 min. The mixture was stirred overnight at room temperature and then quenched with 1 L of methanol. The work-up and separation of excess phenol was carried out by dilution with hexane and extraction against methanol. The conversion was determined by means of ¹ H-NMR (400 MHz in CDCl ₃ ).

H-NMR (400MHz in CDCl3) δ (ppm) = 7.22 (m, 2H), 6.75 (m, 2H), 4.57 (s, 1H), 1.79 (s, 2H), 1.65-0.90 (CH ₃ and CH ₂ , PIB), 0.81 (s, 6H). Example B

1380 g of polyisobutene (M _n 2300 g / mol) were dissolved in 400 g of hexane. 1 13 g of phenol were placed in 200 g of toluene in a 4L HWS vessel with bottom outlet under nitrogen and cooled by means of a refrigerated thermostat to 19 ° C. 15.4 g of BF3-phenol complex was added dropwise to the phenol solution. The polyisobutene solution was added within 4 h at 17-20 ° C. The batch was stirred at room temperature for 48 h and then quenched with a methanol / hexane mixture (1 L / 500 ml). The workup and separation of excess phenol was carried out by extraction against methanol. The conversion was determined by means of ¹ H-NMR (400 MHz in CD 2 Cl 2). example 1

The transesterification was carried out under lean air in a 4L jacketed reactor equipped with an anchor stirrer, a lean air inlet, a separation column and a liquid divider. In this apparatus, 3383 g of a 30% strength solution of a monoethoxylated polyisobutene radical-carrying phenol according to Example 9 were introduced into methyl methacrylate. 0.3 g of methylhydroquinone (MEHQ) and 14.9 g of potassium phosphate were added and the reaction mixture was heated under lean air (2 L / h) at a bath temperature of initially 1 10 ° C. It was set to a pressure of 600 mbar (abs.) And continuously distilled off an azeotrope of methanol and methyl methacrylate, with a bottom temperature of 84 to 87 ° C was established. The reflux ratio was variable 10: 1 to 20: 1 (return: drain). After completion of the reaction, the product was mixed with 15 g Hyflo Super Cel® and 15 g Ambosol® MP 25, via a pressure filter at max. Filtered 2 bar and the reaction mixture concentrated in vacuo. 970 g of product were obtained. The conversion is determined to> 99% via TAI NMR. The stabilizer content was 130 ppm MEHQ (determined by HPLC). ¹ H-NMR (400 MHz in CD 2 Cl 2) δ (ppm) = 7.28 (m, 2H), 6.83 (m, 2H), 6.1 1 (m, 1H), 5.58 (m, 1H) , 4.46 (m, 2H), 4.20 (m, 2H), 1, 94 (s, 3H), 1, 82 (s, 2H), 1.65-0.90 (CH ₃ and CH ₂ , PIB), 0.81 (s, 6H).

 The fluorine content (determined by Combustion IC) was <1 ppm. Example 2 (comparison)

The transesterification was carried out with air in a 0.75 L jacketed reactor equipped with an anchor stirrer, an air inlet, a separation column and a liquid divider. In 50 g of a polyisobutene-bearing phenol, obtained analogously to Example A, and 600 g of methyl methacrylate were initially charged to this apparatus. 0.24 g of methylhydroquinone (MEHQ) and 0.75 g of potassium phosphate were added and the reaction mixture was heated while introducing air (0.3 L / h) at a bath temperature of 15 ° C. It was set a pressure of 600 mbar (abs.) And distilled off continuously MMA with a proportion of methanol, with a bottom temperature of 85 to 86 ° C was established. After 6 h, the reaction mixture was passed through a pressure filter at max. Filtered 2 bar and concentrated in vacuo. The conversion was determined to be 2.5% via 1 H NMR. Example 3

The reaction was carried out in a 500 mL 4-neck round bottom flask with oil bath heating, thermometer, reflux condenser, air inlet and Teflon half-moon stirrer. 145 g of a tempered at 60 ° C, monoethoxylated, carrying a polyisobutene phenol (prepared with 2-methylimidazole as a catalyst according to Example 9) and 33 mg of tert. Butyl hydroxytoluene were presented at a bath temperature of 80 ° C. Under air (about 0.3 L / h) at a bath temperature of 95 ° C 18.9 g of methacrylic anhydride (94%, stabilized with Topanol® A) was added and the bath temperature increased to 100 ° C. After 1.33 h, 80 mg of NaOH was added. After a total of 6 h, the conversion was determined to> 90% via TAI NMR. There were metered in 1, 6 g of methacrylic anhydride and allowed to react for a further 3h at a bath temperature of 100 ° C. The conversion was now determined to> 95% via TAI NMR.

1 1 1 g of the product were mixed with 3 g of n-butanol at 60 ° C and stirred for 1 h. The product phase was extracted 3 x with 30 mL of methanol, the methanolic phases were separated and discarded. The product phase was concentrated in vacuo. The content of methacrylic acid was 1% by weight, methacrylic anhydride is no longer found (determined via 1 H NMR).

Example 4 The reaction was carried out in a 500 ml 4-neck round bottom flask with oil bath heating, thermometer, reflux condenser, introduction of air and Teflon half-moon stirrer. 145 g of a tempered at 60 ° C, monoethoxylated, carrying a polyisobutene phenol (prepared with 2-methylimidazole as a catalyst according to Example 9) and 33 mg of tert. Butyl hydroxytoluene were presented at a bath temperature of 80 ° C. With the introduction of air (about 0.3 L / h) 19.7 g of methacrylic anhydride (94%, stabilized with Topanol® A) were added at a bath temperature of 95 ° C. After 2.75 h, 80 mg of NaOH were added and the bath temperature was raised to 100 ° C. After a total of 5.5 hours, the reaction was stopped and the 80 ° C warm product filled.

 From the product was distilled off in vacuo at 80 ° C to 2.2 mbar methacrylic acid. The sample still contains 2.3% by weight of methacrylic acid (determined via NMR). It was about

50% solution prepared in toluene. The solution was adjusted to pH> 12 with 32% aqueous NaOH and stirred at room temperature for 2 h. 10 g Bentonit® and 10 g Hyflo Super Cel® were added. Subsequently, a pressure filter at max. 2 bar filtered and the product concentrated in vacuo. The conversion was determined to> 95% via TAI NMR. The content of methacrylic acid was <0.25% by weight, methacrylic anhydride is no longer found (determined by NMR). Example 5

The reaction with ethylene carbonate was carried out under nitrogen (about 0.3 L / h) in a 750 mL jacketed reactor equipped with an anchor stirrer, a gas inlet, a separation column and a liquid divider. In this apparatus, 230.2 g of a phenol carrying a polyisobutene moiety of molecular weight 1000 were obtained analogously to Example A, 21, 9 g of ethylene carbonate and 4.1 g of potassium phosphate and heated at a bath temperature of 177-180 ° C, with evolution of CO2. The internal temperature was 169-170 ° C. After 7.5 hours, the mixture was cooled to 60 ° C. 500 g of methyl methacrylate and 0.1 g of MEHQ were added. The reaction mixture was heated with introduction of air (about 0.3 L / h) at a bath temperature of 1 15 ° C. It was set to a pressure of 600 mbar (abs.) And continuously distilled off an azeotrope of methanol and methyl methacrylate, with a bottom temperature of 84 to 87 ° C was established. The distillates were collected and analyzed for their methanol content. After completion of the reaction, the product was passed through a pressure filter at max. Filtered 2 bar and the reaction mixture concentrated in vacuo. The conversion was determined to> 99% via TAI NMR.

Example 6

The transesterification was carried out with introduction of air into a 750 mL jacketed reactor equipped with an anchor stirrer, an air inlet, a separation column and a liquid divider. In this apparatus, 990 g of a 29.3% solution of a monoethoxylated polyisobutene group-carrying phenol according to Example 9 (prepared with 2-methylimidazole as catalyst) in methyl methacrylate were charged. 0.495 g of methylhydroquinone (MEHQ) were added and air was introduced at 95 ° C bath temperature and a vacuum of abs. Distilled off 300 mbar 150 mL of methyl methacrylate.

 150 mL of methyl methacrylate were added and the reaction mixture heated under air (0.3 L / h) at atmospheric pressure with a bath temperature of 120 ° C. 2.3 g Tetraisopropyltita- Nat were added and at a bath temperature of 125 ° C and a vacuum of abs. 700 mbar, an azeotrope of methanol and methyl methacrylate was distilled off continuously, wherein a bottom temperature of 98 ° C is established.

 After completion of the reaction, the reaction mixture was analyzed. The conversion was determined to be 14% via TAI NMR.

Example 7

The reaction was carried out in a 500 ml 4-necked round bottom flask with oil bath heating, thermometer, reflux condenser, water separator, air inlet and Teflon half-moon stirrer. 145 g of a moderately tempered at 60 ° C, slightly ethoxylated, carrying a polyisobutene phenol according to Example 9 (prepared with 2-methylimidazole as catalyst), 100 g of toluene, 10.3 g of methacrylic acid (stabilized with 200 pm MEHQ), 0.76 g of p-toluenesulfonic acid monohydrate and 49 mg of MEHQ were at a bath temperature of 80 ° C. submitted. The reaction mixture was heated. At a bath temperature of 127 ° C, the mixture began to boil. The bath temperature was raised to 140 ° C during the course of the reaction. An additional 1.17 g p-

Added toluenesulfonic acid monohydrate. After a total reaction time of 4.5 hours, no appreciable amount of water was formed (about 0.2 mL of water). The reaction mixture was cooled, and 7.7 g of methanesulfonic acid and a further 5.1 g of methacrylic acid were then added at a bottom temperature of 95 ° C. The bath temperature was readjusted to 140 ° C. In a further 3 h reaction time, a total of 72% of the expected amount of water were removed from the system, in a further hour (total then 8.5 h reaction time) no more water went over. The reaction was stopped.

Example 9

A phenol carrying a polyisobutene radical was obtained analogously to Example A (1 eq.) And ethylene carbonate (1.1 eq.) Was mixed under a nitrogen atmosphere and heated to 100.degree. 2-Methylimidazole (0.6% by weight) were added and the reaction mixture slowly heated to 150 ° C within 5 hours until gas evolution was no longer seen. From 140 ° C a discoloration of the reaction mixture from slightly yellow to brown / black was observed. The conversion was monitored by means of ¹ H-NMR spectroscopy.

EXAMPLE 1 A phenol carrying a polyisobutene radical was obtained analogously to Example A (1 eq.) And ethylene carbonate (1.3 eq.) Were mixed under a nitrogen atmosphere and heated to 170.degree. Potassium phosphate (1.46 wt%) was added and the reaction stirred for 6 hours at 170 ° C until no gas evolution was seen. No discoloration was observed. The conversion was monitored by means of ¹ H-NMR spectroscopy.

Example 12

A polyisobutene-carrying phenol obtained analogously to Example B (1 eq.) And ethylene carbonate (1.3 eq.) Were mixed under a nitrogen atmosphere and heated to 110.degree. Potassium phosphate (1.46% by weight) was added and the reaction stirred at 120-170 ° C under vacuum for 48 hours.

The conversion was monitored by means of ¹ H-NMR spectroscopy.

Example 13 The transesterification was carried out under lean air in a 4L jacketed reactor equipped with a multistage bar stirrer, a lean air inlet, a separation column and a liquid divider. A solution of 450 g of a monoethoxylated phenol carrying a polyisobutene radical according to Example 12 in 1500 g of methyl methacrylate was added to this apparatus. filled with rylate. 0.13 g of methylhydroquinone (MEHQ) and 10.5 g of potassium phosphate were added and the reaction mixture was heated under lean air (0.5 L / h) at a bath temperature of initially 15 ° C. It was set to a pressure of 600 mbar (abs.) And continuously distilled off an azeotrope of methanol and methyl methacrylate, wherein a bottom temperature of 84 ° C was established. The reflux ratio was 20: 1 (reflux: drain). The bath temperature was lowered to 1 10 ° C in the course of the reaction. After completion of the reaction, the reaction mixture was passed through a pressure filter at max. Filtered 2 bar and concentrated in vacuo at 75 ° C bath temperature. There were obtained 449 g of product. The conversion is determined to> 99% via TAI NMR.

homopolymerisations

Solution polymerization: Polymerization example 1:

The polymerization was carried out under a gentle stream of nitrogen in a 4 l jacketed vessel with heating circuit, circulation pump, pilot agitator, long intensive cooler, anchor stirrer and stirring motor. 98.17 g of the product from Example 3 were placed in 391, 32 g of ortho-xylene and heated to 80 ° C. At an internal temperature of 79 ° C 0.26 g of tert-butyl perpivalate (75%) in 19.63 g of ortho-xylene were added within 3 hours. The batch was then heated to 90 ° C. within 15 minutes and 0.18 g of tert-butyl peroctoate in 19.63 g of ortho-xylene were metered in over the course of 30 minutes. The conversion was determined by ¹ H-NMR to 55%. An M _w of 27,700 g / mol (PDI = 12.4) was determined by GPC (RI detector) and an M _w of 25,000 g / mol by GPC (MALLS).

Miniemulsion polymerization: Polymerization example 2:

21, 5 g of the product from Example 3 were first dissolved in 31, 5 g of hexane.

70.88 g of water and 3.68 g of Disponil® FES 27 were premixed in a 250 ml jar and the macromonomer solution added slowly. The resulting pre-emulsion was further emulsified for 50 minutes with vigorous stirring. Subsequently, the preemulsion was sonicated for 2 min at the highest stage with an ultrasound probe at 400 W and 24 kHz. The emulsion was cooled. The miniemulsion was placed in a 250 ml stirrer and made inert by a stream of nitrogen at 150 rpm for 10 min. The internal temperature was adjusted to 70 ° C and 2.15 g of 10% tert. Butyl hydroperoxide solution added. Subsequently, 17.2 g of a 2% sodium acetone bisulfite solution was metered in at a time of 3 hours. The molecular weight (M _w ) of the dispersion obtained was determined by means of GPC (RI detector) to 293,000 g / mol and GPC (UV 275 nm) to 326,000 g / mol. The molecular weight (M _n ) of the dispersion obtained was determined by GPC (Rl detector at 5720 g / mol) and GPC (UV 275 nm) to 6590 g / mol. The low M _n values are attributed to residual monomers. Copolymers

Polymerization Example 3

30 g of the product from Example 3 and 30 g of methyl methacrylate in 207 g of toluene were initially charged and heated to 80 ° C. 5% of a solution of 4 g of tert-butyl perpivalate (75%) in 37.33 g of toluene were added within one minute and stirred for 10 min at 80 ° C (150 U / min) before the remaining 95% of the solution within of 4.5 hours were added. After dosing, stirring was continued for 1, 5 hours at 80 ° C. Polymerization Example 4

45 g of the product from Example 3 and 15 g of methyl methacrylate in 207 g of toluene were initially charged and heated to 80 ° C. 5% of a solution of 4 g of tert-butyl perpivalate (75%) in 37.33 g of toluene were added within one minute and stirred at 80 ° C for 10 min (150 U / min) before the remaining 95% of Solution were added within 4.5 hours. After dosing, stirring was continued for 1, 5 hours at 80 ° C.

Claims

claims

1. Compounds (A) of the formula (I)

wherein

R ¹ to R ^{5 are} each independently selected from the group consisting of hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 -alkyloxy and C 2 -C 8 -socoisobutyl and C 8 -C 3500 -polyisobutenyl,

 R is an alkylene group having from 2 to 10 carbon atoms,

R ^{6 is} hydrogen or methyl,

R ^{7 is} hydrogen, methyl or COOR ⁸ ,

R ^{8 is} hydrogen or Ci-C ₂ o-alkyl and

 n is a positive integer from 1 to 50

with the proviso that at least one of R ¹ to R ^{5 represents} a Cs-Cssoo polyisobutyl or C8-C3500 polyisobutenyl.

Polymers containing, in copolymerized form, at least one compound (A) of the formula (I)

wherein R ¹ to R ^{5 are} each independently selected from the group consisting of hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 -alkyloxy and C 2 -C 8 -socosobutyl and C 8 -C 3500 -polyisobutenyl,

 R is an alkylene group having from 2 to 10 carbon atoms,

R ^{6 is} hydrogen or methyl,

R ^{7 is} hydrogen, methyl or COOR ⁸ ,

R ^{8 is} hydrogen or Ci-C ₂ o-alkyl and

n is a positive integer from 1 to 50

with the proviso that at least one of the radicals R ¹ to R ^{5 is} a Cs-Cssoo-polyisobutyl or C8-C3500 polyisobutenyl and optionally at least one monomer (B) selected from the group consisting of

(B1) other (meth) acrylates than (A),

(B2) other fumaric and maleic acid derivatives than (A),

(B3) alkyl vinyl ether

(B4) styrene and α-methylstyrene

(B5) Acrylonitrile

(B6) vinyl alkanoates and

(B7) (meth) acrylamides.

Compounds or polymer according to any one of the preceding claims, characterized in that in the compounds of formula (I) incorporated Cs-Cssoo-polyisobutyl and Cs-C35oo polyisobutenyl radicals are derived from polyisobutene having a content of terminal double bonds of at least 50 mol%, based on the total number of polyisobutene macromolecules having.

Compounds or polymer according to one of the preceding claims, characterized in that in the compounds of formula (I) incorporated Cs-Cssoo-polyisobutyl and Cs-Cssoo polyisobutenyl radicals are derived from polyisobutene, which is at least 60 wt .-% isobutene contains polymerized. Compounds or polymer according to one of the preceding claims, characterized in that exactly one of the radicals R ¹ to R ^{5 represents} Cs-Cssoo-polyisobutyl or C8-C3500- polyisobutenyl.

Compounds or polymer according to one of the preceding claims, characterized in that R ^{3 is} a Cs-Cssoo-polyisobutyl or Cs-Cssoo polyisobutenyl and the others are not.

Compounds or polymer according to one of the preceding claims, characterized in that the radicals R ¹ to R ⁵ , which do not represent a polyisobutyl or Polyisobute- nylreste are selected from the group consisting of hydrogen, methyl and tert-butyl.

Compounds or polymer according to one of the preceding claims, characterized in that R is selected from the group consisting of 1, 2-ethylene, 1, 2-propylene, 1, 2-butylene, 1-phenyl-1, 2-ethylene and 2-phenyl-1,2-ethylene.

Compounds or polymer according to one of the preceding claims, characterized in that n is 1.

10. Compounds or polymer according to one of the preceding claims, characterized in that R ^{7 is} hydrogen or COOR ⁸ .

Compounds or polymer according to one of the preceding claims, characterized in that the halogen content is not more than 70 ppm by weight.

Compounds according to one of claims 1 or 3 to 1 1, characterized in that the average functionality of α, β-unsaturated carbonyl functions, preferably of (meth) acrylate groups is at least 0.8 and not more than 1, 2.

Polymer according to one of Claims 2 to 11, characterized in that the polymer is a homopolymer which contains exclusively compounds of the formula (I) in copolymerized form.

Polymer according to one of Claims 2 to 11, characterized in that the polymer is a copolymer which also contains at least one other monomer (B) in addition to at least one compound of the formula (I).

15. Polymer according to claim 14, characterized in that the at least one other monomer (B) is selected from the group consisting of monomers (B1), (B3), (B4) and (B7).

16. A process for the preparation of compounds according to claim 1, characterized in that phenols of the formula

with alkylene carbonates of the formula

O

o o

followed by decarboxylation and subsequent esterification with

 (Meth) acrylic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride or by transesterification with (meth) acrylic acid esters, crotonic esters, fumaric esters or maleic acid esters.

Process for the preparation of polymers according to Claim 2, characterized in that the monomer components (A) and optionally (B) are polymerized by means of miniemulsion polymerization.

Use of compounds according to one of claims 1 or 3 to 12 or polymer according to one of claims 2 to 11 or 13 to 15 in the production of adhesives, adhesive raw materials, fuel additives, lubricant additives, as elastomers or as a basic component of sealing and sealing compounds.